Polyols from Natural Oils using the Alkyne Zipper Reaction

Title: POLYURETHANE MATERIALS FORMED FROM UNSATURATED PLANT OILS VIA AN ALKYNE ZIPPER REACTION

Number/Link: US2017/0166679 US2017/0166680

Applicant/Assignee: IBM

Publication Date: 15-june-2017

“Gist”: Oils are turned into alkyne alcohols, ‘zippered’ and oxidized to polyols

Why it is interesting: This is yet  another IBM patent application about interesting, albeit somewhat exotic, chemistry and featuring only “prophetic” examples. In this case unsaturated natural oils are first converted into unsaturated alcohols and then into alkynes by bromination and elimination.  The internal alkynes are then converted to terminal alkynes by an “alkyne zipper reaction” and then into hydroxyl groups by hydroboration and epoxidation/ring-opening. This series of reactions should result in polyols having two primary- and one or more secondary OH groups, useful, for example, for the preparation of sound absorbing foams.

Reaction sequence according to the invention

Polycarbonate PU Foams with Reduced VOC Emissions

Title: POLYURETHANE FOAMS BASED ON POLYETHER CARBONATE POLYOLS

Number/Link: WO2017/085201 (German)

Applicant/Assignee: Covestro

Publication Date: 26-may-2017

“Gist”: Use of urea reduces the formation of propylenecarbonate from polycarbonate polyols

Why it is interesting: Covestry is betting heavily on polyethercarbonate polyols for use in polyurethane foams, using the carbon-negative footprint as a selling point. The use of polyethercarbonate polyols in PU foams can, however, result in the formation of propylenecarbonate resulting from a retro reaction promoted by conventional amine catalysts. Propylenecarbonate will contribute to the total VOC emissions of foams and other materials. According to this invention, the retro reaction can -surprisingly- be prevented or reduced by using urea or urea-derivatives in the foam formulation. In the examples urea and dimethylaminopropylurea are used together with a tin catalyst,  polyethercarbonate polyols and TDI to produce flexible foams with reduced propylenecarbonate content.

Propylenecarbonate

 

 

Matte, Self-Healing Polyurethane Powder Coatings

Title: POLYURETHANE COATING COMPOSITION

Number/Link: WO2017/074835

Applicant/Assignee: Valspar

Publication Date: 4 May 2017

“Gist”: Coating composition comprising isocyanate and two polyester polyols having a similar Tg but a widely different equivalent weight.

Why it is interesting: Conventionally low gloss or “matte” coatings are the result of a microtextured surface achieved by certain fillers or by incompatible polymers and the like. According to this invention “ultra matte” finishes can also -surprisingly- be achieved from a (powder) coating composition comprising a (blocked) isocyanate and a mixture of two polyester polyols. Both polyols have a Tg between 40 and 60ºC prefereably differing not more than 5 to 8ºC, while the OHv of the first polyol is between 150 and 325 and that of the second between 15 and 35.  The ratio between first and second polyol is from about 1:1 to 1:3 w/w. Also surprisingly, the resulting coatings are said to show self-healing properties. An interesting composition but no examples of the polyesters or isocyanates used are given.

Car with matte finish

High Resiliency Polyurethane Foams

Title: HIGH RESILIENCY POLYURETHANE FOAMS MADE WITH HIGH FUNCTIONALITY, HIGH EQUIVALENT WEIGHT POLYOLS WITH MAINLY SECONDARY HYDROXYL GROUPS

Number/Link: WO2017/062150

Applicant/Assignee: Dow

Publication Date: 13 April 2017

“Gist”: Use of high functionality polyols increases the resilience of flex foams

Why it is interesting:  According to this invention the resilience of flexible PU foams can be increased by using, as part of the polyol composition, a random EO/PO polyether polyol which has an equivalent weight of at least 1500, a functionality of  at least 5, a secondary hydroxyl group content of at least 70%, an unsaturation value of at most 0.01 meq/g and an EO content between 5 and 30%.  In the examples, sorbitol initiated polyols are used in both MDI and TDI-based systems, resulting in ball rebound values of up to 60% at densities of about 30 kg/m³.  As I have shown in the past (US5521226) the same (or arguably an even stronger) effect on resilience can be obtained with other high functionality polyols, indicating that the unsaturation value, primary OH content, EO content and equivalent weight are probably not relevant to the resilience increase.

Sorbitol

Bio-Based Acoustic Polyurethane Foam

Patent Title: POLYURETHANE MATERIALS FORMED FROM EPOXIDIZED PLANT OILS

 Number/Link: US2017/0081460

Applicant/Assignee: IBM

Publication date: 23-mar-2017

Gist”: Natural oils are converted into isocyanate-functional polyols and then polymerized

Why it is interesting: Epoxidized vegetable oils are hydrolized and saponified using NaOH, resulting in a mixture of acid-ended polyols. The acid groups are then converted into azides using diphenylphosphoryl azide, which then rearrange into isocyanate groups (Curtius rearrangement).  The isocyanate-ended polyols can be polymerized and further crosslinked using di-isocyanates. The materials are said to be useful as components for acoustic foams, used e.g. in mainframe computers.
This is the second IBM PU patent discussed in this blog. However, I doubt if they have an actual chemistry lab since their examples are “prophetic” rather than real.

IBM

Reaction scheme according to the invbention